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I dunno. She says in the description box that she doesn't recommend it, and she suggests a rinse instead.
My opinion is that your pH balance would become unbalanced, because it would be too much vinegar. The point of the rinse (and mixing it with water) is that it rebalances your hair (because of the pH balance diluting it establishes), which is why a lot of people get that great feeling after the rinse.
I do seem to remember someone that does this. I think she's a member of Nappturality but I might be mistaken.
I personally don't think of ACV as a cleanser so I don't think I could do this. I use ACV at the end of all my washes but couldn't replace my shampoo with it. I also use a very dilute solution 1/4 cup in 2 gallons of water because a very acidic solution could breakdown the protein in your hair, so I prefer to play it safe.
I used to do this all of the time. I think that I will start back. I like the way it cleans my hair and the way it conditions also. It is a natural 2 n 1.